EP3417490B1 - Structures à del servant à réduire la recombinaison non radiative au niveau de parois latérales - Google Patents

Structures à del servant à réduire la recombinaison non radiative au niveau de parois latérales Download PDF

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EP3417490B1
EP3417490B1 EP17737419.6A EP17737419A EP3417490B1 EP 3417490 B1 EP3417490 B1 EP 3417490B1 EP 17737419 A EP17737419 A EP 17737419A EP 3417490 B1 EP3417490 B1 EP 3417490B1
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layer
led
layers
quantum well
quantum
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German (de)
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EP3417490A1 (fr
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David P. Bour
Kelly Mcgroddy
Daniel Arthur HAEGER
James Michael Perkins
Arpan Chakraborty
Jean-Jacques P. Drolet
Dmitry S. Sizov
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Apple Inc
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Apple Inc
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Priority claimed from US15/199,803 external-priority patent/US9601659B2/en
Priority claimed from US15/444,218 external-priority patent/US9865772B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/14—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/14—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
    • H01L33/145—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure with a current-blocking structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
    • H01L33/24—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate of the light emitting region, e.g. non-planar junction

Definitions

  • the present invention relates to light emitting diodes (LEDs). More particularly, embodiments relate to micro LEDs.
  • LEDs are increasingly being considered as a replacement technology for existing light sources. For example, LEDs are found in signage, traffic signals, automotive tail lights, mobile electronics displays, and televisions. Various benefits of LEDs compared to traditional lighting sources may include increased efficiency, longer lifespan, variable emission spectra, and the ability to be integrated with various form factors.
  • OLED organic light emitting diode
  • the emissive layer of the diode is formed of an organic compound.
  • One advantage of OLEDs is the ability to print the organic emissive layer on flexible substrates. OLEDs have been integrated into thin, flexible displays and are often used to make the displays for portable electronic devices such as mobile phones and digital cameras.
  • LED is an inorganic semiconductor-based LED in which the emissive layer of the diode includes one or more semiconductor-based quantum well layers sandwiched between thicker semiconductor-based cladding layers.
  • Some advantages of semiconductor-based LEDs compared to OLEDs can include increased efficiency and longer lifespan.
  • High luminous efficacy, expressed in lumens per watt (lm/W), is one of the main advantages of semiconductor-based LED lighting, allowing lower energy or power usage compared to other light sources.
  • Luminance (brightness) is the amount of light emitted per unit area of the light source in a given direction and is measured in candela per square meter (cd/m 2 ) and is also commonly referred to as a Nit (nt).
  • Luminance increases with increasing operating current, yet the luminous efficacy is dependent on the current density (A/cm 2 ), increasing initially as current density increases, reaching a maximum and then decreasing due to a phenomenon known as "efficiency droop.”
  • IQE internal quantum efficiency
  • Internal quantum efficiency is a function of the quality and structure of the LED device.
  • External quantum efficiency EQE is defined as the number of photons emitted divided by the number of electrons injected.
  • EQE is a function of IQE and the light extraction efficiency of the LED device.
  • the IQE and EQE of an LED device initially increases as operating current density is increased, then begins to tail off as the operating current density is increased in the phenomenon known as the efficiency droop.
  • the efficiency is low due to the strong effect of defects or other processes by which electrons and holes recombine without the generation of light, called non-radiative recombination. As those defects become saturated radiative recombination dominates and efficiency increases.
  • An "efficiency droop" or gradual decrease in efficiency begins as the injection-current density surpasses a characteristic value for the LED device.
  • US2004227142 relates to a light-emitting semiconductor device made of a first reflection film, an active layer, a second reflection film, an electric current spreading layer, a contact layer, and a high resistance region in order.
  • US2003173571 relates to an active semiconductor device, such as an LED, comprising a plurality of semiconductor layers formed on a substrate with one of the layers being an active region, with a current channel formed through this active region, defined by current blocking layers formed on adjacent sides of a designated active region channel where the blocking layers substantially confine the current through the channel.
  • US2008067539 relates to a semiconductor light emitting element including a substrate with upper and lower surfaces, a first nitride semiconductor layer on the upper surface of the substrate, a second nitride semiconductor layer arranged farther from the substrate than the first nitride semiconductor layer, an active layer between the first and second nitride semiconductor layers, and a metal electrode on the second nitride semiconductor layer.
  • the present invention defines an LED according to claim 1. Preferred embodiments are defined in the dependent claims.
  • Embodiments describe LEDs and methods of forming LEDs with various structural configurations to mitigate non-radiative recombination at the LED sidewalls.
  • numerous specific details are set forth, such as specific configurations, dimensions and processes, etc., in order to provide a thorough understanding of the embodiments.
  • well-known semiconductor processes and manufacturing techniques have not been described in particular detail in order to not unnecessarily obscure the embodiments.
  • Reference throughout this specification to "one embodiment” means that a particular feature, structure, configuration, or characteristic described in connection with the embodiment is included in at least one embodiment.
  • the appearances of the phrase "in one embodiment” in various places throughout this specification are not necessarily referring to the same embodiment.
  • the particular features, structures, configurations, or characteristics may be combined in any suitable manner in one or more embodiments.
  • the terms “above”, “over”, “to”, “between”, “spanning” and “on” as used herein may refer to a relative position of one layer with respect to other layers.
  • One layer “above”, “over”, “spanning” or “on” another layer or bonded “to” or in “contact” with another layer may be directly in contact with the other layer or may have one or more intervening layers.
  • One layer “between” layers may be directly in contact with the layers or may have one or more intervening layers.
  • LEDs which may be micro LEDs, that include certain structural configurations to mitigate non-radiative recombination at the LED sidewalls.
  • the sidewalls for emissive LEDs may represent non-radiative recombination sinks for injected carriers. This may be due to the sidewalls being characterized by unsatisfied bonds, chemical contamination, and structural damage (particularly if dry-etched). Injected carriers recombine non-radiatively at states associated with these defects. Thus, the perimeter of an LED may be optically dead, and the overall efficiency of the LED is reduced.
  • This non-radiative recombination can also be a result of band bending at the surface leading to a density of states were electrons and holes can be confined until they combine non-radiatively.
  • the characteristic distance over which the sidewall surface effect occurs is related to the carrier diffusion length, which may typically be 1-10 ⁇ m in some applications in accordance with embodiments.
  • the efficiency degradation is particularly severe in micro LEDs in which the LED lateral dimensions approach the carrier diffusion length.
  • Such non-radiative recombination may have a significant effect on LED device efficiency, particularly when the LED is driven at low current densities in the pre-droop region of its characteristic internal quantum efficiency (IQE) curve where the current is unable to saturate the defects.
  • IQE characteristic internal quantum efficiency
  • sidewall passivation techniques, current confinement structures, and combinations thereof are described such that the amount of non-radiative recombination near the exterior or side surfaces of the active layer can be reduced and efficiency of the LED device increased.
  • micro LED as used herein may refer to the descriptive size, e.g. length or width, of the LED.
  • micro may be on the scale of 1 ⁇ m to approximately 300 ⁇ m, or 100 ⁇ m or less in many applications. More specifically, in some embodiments, “micro” LEDs may be on the scale of 1 ⁇ m to 20 ⁇ m, such as 10 ⁇ m or 5 ⁇ m where the LED lateral dimensions approach the carrier diffusion length.
  • embodiments are not necessarily so limited, and that certain aspects of the embodiments may be applicable to larger, and possibly smaller size scales.
  • the sidewall surface of the LED including at least the active layer is passivated in order to restore the radiative efficiency of the LEDs.
  • a variety of different structural configurations are disclosed for sidewall passivation including various regrowth and diffusion techniques.
  • Such sidewall passivation may have several effects depending upon the particular passivation technique. One effect may be to preserve the lattice structure and minimize defects at the LED sidewalls and/or active layer edges, thereby mitigating the effects of non-radiative combination at the LED sidewalls and/or active layer edges.
  • Another effect may be to move the LED sidewalls and/or active layer edges to an interior of the p-n diode layer, such that the current injection path is confined internally with the p-n diode layer away from the p-n diode layer sidewalls where defects might be present.
  • an in-situ etch is performed to form the LED sidewalls adjacent the active layer. For example, this is performed in an MOCVD epitaxial growth reactor. In this manner, the purely chemical etch introduces minimal structural damage compared to dry etching techniques such as ICP/RIE.
  • the in-situ etch is then followed immediately by in-situ epitaxial regrowth of the sidewall passivation layer on the newly-created surface. Since there is no air exposure, oxidation of the sidewall is eliminated. Since the passivation layer is grown epitaxially on the LED sidewalls, any dangling bonds at the free surface (prior to regrowth) are satisfied. Thus, the lattice structure is preserved and defects are minimized at the LED sidewalls. In this manner, the surface recombination at the LED sidewalls may be mitigated.
  • diffusion techniques result in moving the LED sidewalls and/or lateral edges of the active layer (e.g. including one or more quantum wells) to an interior of the p-n diode layer.
  • the active layer e.g. including one or more quantum wells
  • diffusion techniques result in moving the LED sidewalls and/or lateral edges of the active layer (e.g. including one or more quantum wells) to an interior of the p-n diode layer.
  • a passivation layer within the p-n diode layer and laterally around the internally confined active layer, a barrier is created to the lateral carrier diffusion from the active layer.
  • Such a barrier may prevent lateral carrier diffusion from the active layer edges to the adjacent p-n diode layer sidewalls where defects might be present.
  • the passivation layer may be narrower than the above mentioned carrier diffusion length of 1-10 ⁇ m in some embodiments.
  • epitaxial growth of the sidewall passivation layer is performed ex-situ. For example, this may be performed after vapor etching the LED sidewalls for a GaN-based LED.
  • sidewall passivation is accomplished by diffusion into the exposed p-n diode layer sidewalls to displace the edges of the active layer into an interior of the p-n diode layer.
  • the active layer is formed within the interior of the LED by diffusion. In this manner, the current injection path is directed internally through the LED and away from the sidewalls.
  • LED mesas are selectively grown followed by in-situ growth of a sidewall passivation layer to cover the active layer edges.
  • the LED active layer and cladding layers are grown over a patterned substrate such that n-doping and p-doping within the layers is dependent upon orientation of the surface.
  • p-dopants and n-dopants are simultaneously flowed into the chamber where they are preferentially deposited on different exposed planes.
  • the active layer is selectively etched to produce a notch between the n-doped cladding layer (or current spreading layer) and the p-doped cladding layer (or current spreading layer). This notch is then filled by mass transport, resulting in edges of the active layer being confined to an interior of the p-n diode layer.
  • the bandgap energy at the p-n diode layer sidewalls is increased by surface conversion.
  • the p-n diode layer sidewalls may be exposed to a vapor chemistry at high temperature in which a group V species evaporates (e.g. As) and is replaced by a group V vapor species (e.g. P).
  • a group V species evaporates (e.g. As) and is replaced by a group V vapor species (e.g. P).
  • deposition conditions and layer strain are controlled in order to take advantage of the miscibility gap of the deposition components in the active layer and form a non-homogenous composition in which certain species segregate and form clumps. In this manner, a quantum dot effect is achieved in which lateral spreading across the active layer is reduced, and resultant sidewall recombination at the surface is reduced.
  • nanopillars are formed by selective growth or patterning.
  • the formation of nanopillars may contribute to the quantum dot effect that takes advantage of carrier localization at the dot or pillar, which may reduce lateral spreading across the active layer.
  • the formation of nanopillars may additionally increase the surface area within the active layer, thereby lessening the relative surface area of the active layer at the LED sidewalls.
  • selective diffusion is utilized to create vacancies, causing interdiffussion at the p-n diode layer sidewalls. In this manner, a higher bandgap energy is created at the sidewall surfaces that effectively confines the active layer to an interior of the p-n diode layer.
  • atomic layer deposition is utilized to form a sidewall passivation layer (e.g. Al 2 O 3 ) surrounding p-n diode layer sidewalls.
  • ALD atomic layer deposition
  • any of the above structural configurations may be combined with a current spreading layer pillar structure.
  • either of the p-doped or n-doped layers in a p-n configuration may be considered as current spreading layers.
  • either of the current spreading layers is patterned such that it is narrower than the active layer including the p-n diode.
  • the bottom current spreading layer e.g. p-doped layer
  • the current injection area within the active layer is modified by the relationship of the areas of the bottom current spreading layer pillar and top current spreading layer.
  • the current injection area is reduced as the area of the bottom current spreading layer pillar configuration is reduced. In this manner, the current injection area can be confined internally within the active layer away from external or side surfaces of the active layer.
  • a current spreading layer pillar structure it is possible to design an LED in which a top surface area of the top surface of the p-n diode layer is larger than a surface area of the current confinement region within the active layer. This enables larger LED devices to be fabricated, which may be beneficial for transferring the LED devices using an electrostatic transfer head assembly, while also providing a structure in which the confined current injection area results in an increased current density and increased efficiency of the LED device, particularly when operating at injection currents and injection current densities below or near the pre-droop region of the LED device IQE curve.
  • FIG. 1A a cross-sectional side view illustration is provided of a bulk LED substrate 100 including a p-n diode layer 115 formed on the growth substrate in accordance with an example not forming part of the invention.
  • the p-n diode layer 115 illustrated in FIG. 1A may be designed for emission of primary red light (e.g. 620-750 nm wavelength), primary green light (e.g. 495-570 nm wavelength), or primary blue light (e.g. 450-495 nm wavelength), though embodiments are not limited to these exemplary emission spectra.
  • the p-n diode layer 115 may be formed of a variety of compound semiconductors having a bandgap corresponding to a specific region in the spectrum.
  • the p-n diode layer 115 can include one or more layers based on II-VI materials (e.g. ZnSe) or III-V materials including III-V nitride materials (e.g. GaN, AlN, InN, InGaN, and their alloys), III-V phosphide materials (e.g. GaP, AlGaInP, and their alloys), and III-V arsenide alloys (AlGaAs).
  • the growth substrate 100 may include any suitable substrate such as, but not limited to, silicon, SiC, GaAs, GaN, and sapphire.
  • the p-n diode layer 115 can include a variety of configurations depending upon application.
  • the p-n diode layer 115 includes a current spreading layer 104 of a first dopant type (e.g. n-doped), a current spreading layer 112 of opposite dopant type (e.g. p-doped), and an active layer 108 between the current spreading layers 104, 112.
  • the active layer 108 may be a single quantum well (SQW) or multi-quantum well (SQW) layer.
  • a reduced number of quantum wells may offer more resistance to lateral current spreading, higher carrier density, and aid in confining current internally within the completed LED.
  • active layer 108 includes a SQW. In an embodiment, active layer 108 is a MWQ structure with less than 10 quantum well layers. In an embodiment, active layer 108 is a MWQ structure with 1-3 quantum wells. Additional layers may optionally be included in the p-n diode layer 115. For example, cladding layers 106, 110 may be formed on opposite sides of the active layer 108 to confine current within the active layer 108 and may possess a larger bandgap than the active layer 108. Cladding layers 106, 110 may be doped to match the doping of the adjacent current spreading layers 104, 112.
  • cladding layer 106 is doped with an n-type dopant
  • cladding layer 110 is doped with a p-type dopant, or vice versa.
  • the current spreading layers may be functionally similar to cladding layers.
  • the p-n diode layer 115 is design for emission of red light, and the materials are phosphorus based.
  • the layers forming the p-n diode layer 115 may include AlInP, AlInGaP, AlGaAs, GaP, and GaAs.
  • current spreading layer 104 includes n-AlInP or n-AlGaInP
  • cladding layer 106 includes n-AlInGaP
  • cladding layer 110 includes p-AlGaInP
  • current spreading layer 112 includes p-GaP or p-AlInP.
  • Quantum well 108 may be formed of a variety of materials, such as but not limited to, AlGaInP, AlGaAs, and InGaP.
  • a suitable growth substrate 102 may include, but not limited to, silicon, SiC, and GaAs.
  • the p-n diode layer 115 is designed for emission of blue or green light, and the materials are nitride based.
  • the followed listing of materials for blue or green emission is intended to be exemplary and not limiting.
  • the layers forming the p-n diode layer 115 may include GaN, AlGaN, InGaN.
  • current spreading layer 104 includes n-GaN
  • cladding layer 106 is optionally not present
  • cladding layer 110 includes p-AlGaN
  • current spreading layer 112 includes p-GaN.
  • Quantum well 108 may be formed of a variety of materials, such as but not limited to, InGaN.
  • a suitable growth substrate 102 may include, but is not limited to, silicon and sapphire.
  • cladding layer 106 may not be necessary for nitride based LEDs due to internal piezoelectric and spontaneous polarization fields.
  • FIGS 1B-1F are cross-sectional side view illustrations of a one-sided process sequence for fabricating an array of LEDs.
  • an array of conductive contacts 116 are formed over the p-n diode layer 115, and the p-n diode layer 115 is etched to form trenches 118 between mesa structures 120.
  • Conductive contacts 116 may include a multiple layer stack. Exemplary layers can include electrode layers, mirror layers, adhesion/barrier layers, diffusion barriers, and a bonding layer for bonding the completed LEDs to a receiving substrate.
  • the conductive contacts 116 are formed on a p-doped current spreading layer 112, and are functionally p-contacts.
  • Etching can be performed utilizing a suitable technique such as dry etching or wet etching.
  • trenches are not formed completely through the n-doped current spreading layer 104.
  • trenches are formed completely through the n-doped current spreading layer 104.
  • pillars are partially through the p-doped current spreading layer 112 (see FIG. 3 ).
  • the structure formed in FIG. 3 can be made using a one-sided process, or a two-sided process where the pillars are formed using the one-sided process, and the mesa structures are etched after transferring to the receiving substrate using a two-sided process.
  • a sacrificial release layer 122 may be formed over the patterned p-n diode layer 115, and then patterned to form openings 124 over the conductive contacts 116.
  • the sacrificial release layer 122 may be formed of an oxide (e.g. SiO 2 ) or nitride (e.g. SiN x ), though other materials may be used which can be selectively removed with respect to the other layers.
  • the height, width, and length of the openings 124 will correspond to the height, length, and width of the stabilization posts to be formed, and resultantly the adhesion strength that must be overcome to pick up the array of LEDs (e.g. micro LEDs) that are poised for pick up on the array of stabilization posts.
  • the patterned structure on the growth substrate 102 is bonded to a carrier substrate 140 with an adhesive bonding material to form stabilization layer 130.
  • the adhesive bonding material is a thermosetting material such as benzocyclobutene (BCB) or epoxy.
  • BCB benzocyclobutene
  • the portion of the stabilization material that fills openings 124 corresponds to the stabilization posts 132 of the stabilization layer, and the portion of the stabilization material that fills the trenches 118 becomes the stabilization cavity sidewalls 134 of the stabilization layer.
  • the growth substrate may be removed utilizing a suitable technique such as laser lift-off, etching, or grinding to expose the p-n diode layer 115. Any remaining portions of the n-doped current spreading layer 104 connecting the separate mesa structures 120 may then be removed using etching or grinding to form laterally separate p-n diode layers 115. A top conductive contact layer 142 may then be formed over each laterally separate p-n diode layer resulting LED 150.
  • FIGS. 1E and 1F represent alternative structures that may be obtained, depending upon the amount of material removed after removal of the growth substrate 102 and etching or grinding back to expose the mesa structures 120.
  • the p-n diode layer 115 is patterned to form mesa structures 120 prior to be being transferred to a carrier substrate 140.
  • LEDs in accordance with embodiments can be fabricated utilizing a two-sided process in which the p-n diode layer 115 is transferred from the growth substrate to a carrier substrate 140, followed by patterning of the p-n diode layer to form mesa structures 120.
  • a variety of processing techniques can be used to obtain similar final structures including sidewall passivation techniques, current confinement techniques, and combinations thereof. Accordingly, while the LEDs structures in the following description are all described using a one-sided processing sequence, this is illustrative and not meant to be limiting.
  • FIGS. 2-3 are exemplary cross-sectional side view illustrations of LEDs that may be formed using a one-sided process similar to the one described with regard to FIGS. 1B-1F .
  • FIG. 2 is a cross-sectional side view illustration of an LED including active layer 108 edges 151 along sidewalls 153 of the p-n diode layer.
  • FIG. 3 is a cross-sectional side view illustration of an LED with a bottom current spreading layer 112 pillar structure with a reduced width compared to the active layer 108.
  • the current spreading layer pillar 112 may be function to internally confine the current injection path away from the active layer 108 edges 151 along sidewalls 153 of the p-n diode layer.
  • edges 151 of the active layer 108 may be damaged as a result of etching the sidewalls 153 of the p-n diode layer 115 mesa structures 120. Accordingly, edges of the active layer may be a site for non-radiative recombination.
  • various structural configurations are described to mitigate non-radiative recombination at the edges of the active layer.
  • the various structures may include sidewall passivation techniques, current confinement techniques, and combinations thereof.
  • FIGS. 4A-4E cross-sectional side view illustrations are provided for a method of forming an LED with an in-situ regrown p-n junction sidewall passivation layer in accordance with an example not forming part of the invention.
  • the particular processing sequence illustrated in FIGS. 4A-4E may be generic for LEDs of any emission color, including red, blue, and green and may include any of the p-n diode layer 115 configurations described above with regard to FIG. 1A .
  • the processing sequence illustrated in FIGS. 4A-4E may include in-situ etching and regrowth.
  • a mask 117 is formed over the p-n diode layer 115 to etch trenches 118 at least partially into the doped current spreading layer 104.
  • the mask 117 may be formed with a dielectric material, such as SiO 2 , that can survive the high temperatures and aggressive etch chemistries associated with the etch and regrowth processes.
  • the etching process is a purely chemical etch that is performed in an metal organic chemical vapor deposition (MOCVD) chamber.
  • trenches 118 are formed by a first partial dry etch, and then the wafer is transferred to an MOCVD chamber to complete etching of the trenches 118.
  • the final etched surfaces are conditioned by etching in the MOCVD chamber and physical damage created during the dry etching operation is removed by the chemical etching in the MOCVD chamber.
  • exemplary dry etching techniques that may be used include reactive ion etching (RIE), electro-cyclotron resonance (ECR), inductively coupled plasma reactive ion etching (ICP-RIE), and chemically assisted ion-beam etching (CAIBE).
  • the dry etching chemistries may be halogen based, containing species such as Cl 2 , BCl 3 , or SiCl 4 .
  • the etching temperature within the MOCVD chamber may additionally be at an elevated temperature, such as 400 °C - 700 °C.
  • the specific etching chemistry may include a combination of a corrosive etchant and group V decomposition suppressant to stabilize the group V element, and suppress decomposition that may otherwise occur at the elevated etching temperature.
  • the LED is designed for red emission, and the p-n diode layer 115 is phosphorus based.
  • the etching chemistry includes a corrosive etchant such as HCl or Cl 2 , and a group V decomposition suppressant such as PH 3 .
  • the LED is designed for green or blue emission, and the p-n diode layer 115 is nitride-based.
  • the etching chemistry includes a corrosive etchant such as HCl, Cl 2 , or H 2 (or combinations thereof), and a group V decomposition suppressant such as NH 3 .
  • a passivation layer 402 is epitaxially regrown in the trenches 118.
  • the regrowth of passivation layer 402 is performed in-situ in the MOCVD chamber immediately after etching trenches 118, and without exposure to air or removal from the MOCVD chamber. Since the passivation layer 402 is epitaxially regrown on a pristine surface, it serves as surface passivator to the p-n diode, and specifically the active layer 108. In accordance with embodiments, the passivation layer 402 has a higher bandgap than the individual layers within the p-n diode layer 115.
  • the passivation layer 402 may also be p-type.
  • the passivation layer 402 may be p-doped with Mg or Zn dopants.
  • the passivation layer may be AlInGaP:Mg,Zn.
  • the passivation layer 402 may be p-doped with Mg.
  • the passivation layer may be AlGaN:Mg.
  • the passivation layer 402 may be made insulating with C or Fe dopants.
  • the passivation layer may be AlGaN:C,Fe.
  • Mask 117 may then be removed, followed by the formation of conductive contacts 116 on the exposed portion of the p-n diode layer 115 (e.g. p-doped current spreading layer 112) as illustrated in FIG. 4C .
  • Trenches 410 are then etched through the passivation layer 402 and p-n diode layer 115 to form mesa structures 420 as illustrated in FIG. 4D .
  • dry etching techniques may now be used.
  • trenches 410 are wet etched to reduce the surface damage to sidewalls of the p-n diode layer 115, which become p-n diode layer sidewalls 153 of the LED.
  • a combination of dry etching followed by wet etching is used.
  • the mesa structures 420 may then be transferred to the carrier substrate 140 and top conductive contact 142 formed similarly as discussed above with regard to FIGS. 1B-11F .
  • FIG. 4F is a cross-sectional side view illustration of an LED with an in-situ regrown p-n junction sidewall passivation layer in accordance with an example not forming part of the invention.
  • the passivation layer 402 laterally surrounds the LED sidewalls 151, which also correspond to the edges of the active layer 108, and the p-n diode layer sidewalls 153.
  • the passivation layer 402 is epitaxially grown, thereby satisfying all bonds at the original surface. In this manner, the surface recombination is minimized and the LED's radiative efficiency is restored.
  • the regrown p-n junction passivation layer 402 may be formed of a high bandgap material, and therefore has a higher turn-on voltage (V o2 ) than the emitting p-n junction V o1 , i.e. V o2 > V o1 .
  • V o2 turn-on voltage
  • the current will preferentially flow through the intended region which emits light.
  • FIGS. 5A-5H are cross-sectional side view illustrations of a method of forming an LED with vapor etched sidewalls and a regrown sidewall passivation layer in accordance with an example not forming part of the invention.
  • the processing sequence illustrated in FIGS. 5A-5H is directed toward green or blue emitting, nitride-based LEDs.
  • AlGaN cladding layer 106 may be omitted due to internal piezoelectric and spontaneous polarization fields.
  • cladding layer 110 may additionally omitted from the p-n diode layer illustrated in FIG. 5A .
  • micro LEDs in accordance with embodiments may operate at lower currents than conventional LEDs.
  • the AlGaN cladding layers 106, 110 may not be necessary in either side of the quantum well 108.
  • the p-n diode layer 115 includes a p-GaN layer 112, InGaN active layer 108, and n-GaN layer 104.
  • a thin semiconductor mask layer 513 is formed over the p-n diode layer 115.
  • semiconductor mask layer 513 is formed of AlGaN.
  • trenches 118 are etched at least partially through the p-n diode layer 115 to form the mesa structures 520. Initially RIE/ICP etching may be used to etch a shallow trench 118 through the AlGaN semiconductor mask layer 513. This may be followed by a H 2 + NH 3 vapor etching at high temperature to complete the etching of trenches 118.
  • H 2 + NH 3 vapor etching may result in minimal structural damage compared to RIE/ICP etching, and can be etched at a planar rate of approximately 200 nm/hour, forming vertical m-plane sidewalls. Since, AlGaN cladding layers 106, 110 are not present they will not interfere with or block the H 2 + NH 3 vapor etching. When the trenches are properly oriented, vertical sidewalls may be obtained.
  • an epitaxially regrown passivation layer 502 can be formed over the patterned p-n diode layer and semiconductor mask layers 513.
  • passivation layer 502 may be regrown p-GaN.
  • epitaxial regrowth of passivation layer 502 is ex-situ from the vapor etching of trenches 118.
  • the epitaxially regrown passivation layer 502 may match the lattice structure of the vapor etched sidewalls with minimal defects.
  • the passivating layer 502 is epitaxially regrown in-situ, i.e., immediately after vapor etch in an MOCVD reactor, so that there is no air-exposure. Trenches 518 are then etched through epitaxially regrown passivation layer 502, and the structure transferred to a carrier substrate 140 as previously described.
  • FIG. 51 is a cross-sectional side view illustration of an LED with a regrown sidewall passivation layer in accordance with an embodiment.
  • the LED 550 includes passivation layer 502 formed around the sidewalls 153 and underneath the p-n diode layer 115, and the bottom conductive contact 116 is formed on the p-doped passivation layer 502.
  • the passivation layer 502 does not completely cover sidewalls of the n-doped current spreading layer 104, and does not reach the top surface of the p-n diode layer. In this manner, a p-n junction is created at the interface of 502-104 which has a higher turn-on voltage than at the active layer 108, and current preferentially flows through the intended region which emits light.
  • the passivation layer 502 laterally surrounds the active layer 108 within the LED 550 such that edges 151 of the active layer 108 are passivated by the passivation layer 502.
  • FIGS. 6A-6E are cross-sectional side view illustrations of a method of forming an LED with a diffused sidewall passivation layer in accordance with an example not forming part of the invention.
  • FIGS. 6A-6E are directed toward phosphorus based LEDs designed for emission of red light.
  • p-n diode layer 115 includes any of the compositions discussed above with regard to FIG. 1A .
  • the p-n diode layer 115 is patterned to form trenches 118 at least partially through current spreading layer 104.
  • a mask 605 may be used to define the mesa structures 120 during etching of the trenches 118.
  • a diffusion operation is performed to diffuse a species into the sidewalls of the mesa structures 120 and form passivation layer 602. Diffusion may additionally occur on the exposed surface of the p-n diode layer 115 between the mesa structures 120, and optionally on top of the mesa structures 120 if the mask 605 has been removed.
  • the diffusion and formation of passivation layer 602 displaces the previously exposed p-n junction (and active layer 108) into an interior of the LED. As a result, the p-n junction does not intersect the surface, and is formed of undamaged material. In one particular embodiment, an intermixed heterostructure is created.
  • the AlInGaP heterostructure is grown under conditions and substrate orientation to spontaneously produce an ordered alloy crystal structure (CuPt-type ordering which comprises a GaAlP-InP monolayer superlattice on the (111) crystal planes).
  • the ordered alloy cladding layer 106 e.g. n-AlInGaP
  • quantum well layer 108 InGaP
  • cladding layer 110 e.g. p-AlGaInP
  • the above-described diffusion process may randomize this alloy, thereby raising its bandgap energy.
  • the randomized sidewall, with higher bandgap energy naturally forms a potential barrier which suppresses sidewall recombination.
  • the randomized AlInGaP forms a passivation layer 602.
  • a variety of methods may be employed to form the passivation layer 602, including implantation, vapor diffusion, and coating a source layer followed by heating (solid source diffusion).
  • a p-dopant such as Zn or Mg is implanted and/or diffused to change the n-type layers (110, 112) to p-type in the passivation layer 602.
  • another species such as Fe, Cr, Ni, or another dopant can be added to make the passivation layer 602 semiinsulating.
  • He or H can be implanted, also known as proton bombardment or proton implantation. The damage created by proton bombardment in turn increases the resistivity of the implanted passivation layer 602. Implantation energy may be controlled so as to not create too much damage so as to act as a significant source for non-radiative recombination.
  • FIG. 6F is a cross-sectional side view illustration of an LED with a diffused sidewall passivation layer in accordance with an embodiment.
  • the LED 650 includes passivation layer 602 formed within the sidewalls 153 of the p-n diode layer 115.
  • the passivation layer 602 does not completely cover sidewalls of the n-doped current spreading layer 104, and does not reach the top surface of the p-n diode layer.
  • the passivation layer 602 laterally surrounds the active layer 108 within the LED 650 such that the LED sidewalls 151 (corresponding to the edges of the active layer 108) are internally confined within the p-n diode layer sidewalls 153 that have been converted to passivation layer 602.
  • FIGS. 7A-7E are cross-sectional side view illustrations of a method of forming a p-n junction within an LED by selective diffusion in accordance with an example not forming part of the invention.
  • the epitaxial layer 715 differs slightly from the p-n diode layer 115 illustrated in FIG. 1A in that layers 710, 712 are n-doped rather than p-doped (layers 110, 112).
  • the starting epitaxial layer 715 includes an n/n heterostructure, and a p-n junction is not yet formed.
  • epitaxial layer 715 includes (n)-AlInP current spreading layer 104, (n)-AlInGaP cladding layer 106, quantum well layer 108, (n-)- AlGaInP cladding layer 710, and (n-) AlInP current spreading layer 712.
  • the p-n junction is formed by diffusion of a p-dopant such as Mg or Zn into current spreading layer 712, and cladding layer 710. Diffusion can be from a solid source, or vapor as described above with regard to FIG. 6A-6E .
  • p-doped region 702 is diffused into the cladding layer 710 and current spreading layer 712 as described above, stopping before the p-dopant encroaches into the active layer 108.
  • an insulating layer 711 is formed over the epitaxial layer 715.
  • Insulating layer 711 may be formed of a variety of materials, including SiO 2 and SiN x .
  • openings are formed in the insulating layer 711, and conductive contacts 116 are formed over the openings, and trenches 118 are then etched through the insulating layer 711 and epitaxial layer 715 to form mesa structures 720.
  • the processing sequence illustrated in FIGS. 7D-7E may then be similar to that described above with regard to FIGS. 1B-1F to form LEDs 750.
  • FIG. 7F is a cross-sectional side view illustration of an LED with a selectively diffused p-n junction in accordance with an embodiment.
  • the LED 750 includes an internally confined p-doped region 702 extending through (n-) doped current spreading layer 712, and (n-) doped cladding layer 710.
  • Insulating layer 711 may optionally be formed in order to cover the junction between p-doped region 702 and (n-) doped current spreading layer 712 so that the bottom conductive contact 116 does not make contact with the (n-) doped current spreading layer 712.
  • the current injection region into the active layer 108 is confined internally within the LED by the p-doped region 702.
  • FIGS. 8A-8E are cross-sectional side view illustrations of a method of forming an LED with a diffused transverse junction in accordance with an example not forming part of the invention.
  • epitaxial layer 815 illustrated in FIG. 8A is identical to the epitaxial layer 715 illustrated in FIG. 7A , with layers 810, 812 corresponding to layers 710, 712.
  • the processing sequence illustrated in FIGS. 8A-8E is substantially similar to that illustrated in FIGS. 7A-7E with the difference being that the p-doped regions 802 are formed through layers 812, 810, 108, 106, and partially into current spreading layer 104.
  • FIG. 8F is a cross-sectional side view illustration of an LED 850 with a diffused transverse junction in accordance with an example not forming part of the invention.
  • the p-n junction becomes a lateral junction formed within the active layer 108.
  • the current injection region into the active layer 108 is confined internally within the LED by the p-doped region 802.
  • the p-n junction is transverse, and confined internally within the LED 850.
  • FIGS. 9A-9E are cross-sectional side view illustrations of a method of forming an LED with selective area grown and in-situ growth of a sidewall passivation layer in accordance with an example not forming part of the invention.
  • the method illustrated in FIGS. 9A-9E is directed toward phosphorus based LEDs designed for emission of red light, and having a cubic crystal structure.
  • the method illustrated in FIGS. 9A-9E may be applicable to other types of crystal structures, and may result in more complex sidewall shapes.
  • a patterned mask layer 111 is formed over a growth substrate 102.
  • the patterned mask layer 111 is formed directly on a growth substrate 102 that will eventually be removed.
  • the patterned mask layer 111 is formed on a partially formed current spreading layer 104.
  • Mesa structures 920 may then be selectively grown in the pre-defined openings within the patterned mask layer 111.
  • Mesa structures 920 may include epitaxial layers similar to those described above with regard to p-n diode layer 115 of FIG. 1A for emission of red light.
  • selective area growth results in no-growth (111) sidewalls, on a near-(100) surface.
  • an in-situ sidewall passivation layer 902 is grown (in-situ with growth of the mesa structures).
  • the passivation layer includes AlInP, which may be p-doped.
  • the passivation layer 902 is grown in-situ, immediately following formation of the mesa structures 920, without removing from the MOCVD reactor. The passivation layer 902 grows conformally by reducing the growth temperature to avoid evaporation or migration of the deposition species.
  • conductive contacts 116 are formed and the processing sequence may be performed similarly as described above with regard to FIGS. 1B-1F to form LEDs 950.
  • FIG. 9F is a cross-sectional side view along a x-direction (111) plane of a selectively grown LED with an in-situ grown sidewall passivation layer in accordance with an example not forming part of the invention.
  • FIG. 9G is a cross-sectional side view along a y-direction (111) plane of a selectively grown LED with in-situ grown sidewall passivation layer in accordance with an example not forming part of the invention.
  • the passivation layer 902 may be similar to that described above with regard to FIG. 51.
  • the LED 950 includes passivation layer 902 formed around the sidewalls 153 and underneath the p-n diode layer 115, and the bottom conductive contact 116 is formed on the p-doped passivation layer 902.
  • the passivation layer 902 does not completely cover sidewalls of the n-doped current spreading layer 104, and does not reach the top surface of the p-n diode layer. In this manner, a p-n junction is created at the interface of 902-104 in which has a higher turn-on voltage than at the active layer 108, and current preferentially flows through the intended region which emits light.
  • the passivation layer 902 laterally surrounds the active layer 108 within the LED 950 such that edges 151 of the active layer 108 are passivated by the passivation layer 902.
  • FIGS. 10A-10D are cross-sectional side view illustrations of a method of forming an LED with a regrown sidewall passivation layer in accordance with an example not forming part of the invention.
  • the method illustrated in FIGS. 10A-10D is directed toward phosphorus based LEDs (e.g. AlGaInP) designed for emission of red light, and having a cubic crystal structure.
  • phosphorus based LEDs e.g. AlGaInP
  • a p-n diode layer 115 is formed on a growth substrate 102, similarly as described above with regard to FIG. 1A .
  • the p-n diode layer 115 is then wet chemical etched to form (111) sidewalls. Referring to FIG.
  • passivation layer 1002 includes GaN, which can be insulating compared to the p-n diode layer 115. Alternatively, it may be grown p-type. Because the sidewalls have a (111) crystal surface orientation, they serve as a proper seed surface for epitaxial growth of the hexagonal structure AlGaN. Thereby the quality of the regrown epitaxial interface is improved to reduce surface recombination.
  • this structure may be formed entirely in an in-situ process, where the (111) sidewall mesa structures are formed by selective growth as described with regard to FIGS. 9A-9G , then immediately passivated in-situ by epitaxial growth of insulating or p-type GaN.
  • the mask layer 1010 is removed and the structure is processes similarly as described above with regard to FIGS. 1B-1F to form LEDs 1050.
  • FIG. 10E is a cross-sectional side view along a x-direction (111) plane of an LED with a regrown sidewall passivation layer in accordance with an example not forming part of the invention.
  • FIG. 10F is a cross-sectional side view along a y-direction (111) plane of an LED with a regrown sidewall passivation layer in accordance with an embodiment.
  • the passivation layer 1002 is formed around the p-n diode layer sidewalls 153 (also corresponding to the LED sidewalls 151). Since the passivation layer 1002 is epitaxially grown, the bonds are satisfied at the LED sidewalls 151. In this manner, the surface recombination is minimized.
  • the p-n diode layer 115 can be wet etched and then transferred to a chamber for epitaxial growth without oxidation of the exposed layers after wet etching.
  • FIGS. 10G-10H are similar to FIGS. 10E-10F , with a difference being that the LEDs are patterned to include a wide top current spreading layer 104. In this manner, the top conductive contact 104 can be made larger, with less risk of making direct contact through the passivation layer 1002.
  • FIGS. 11A-11D cross-sectional side view illustrations are provided for a method of forming an LED p-n junction with orientation dependent doping in accordance with an example not forming part of the invention.
  • FIG. 11A is a close up cross-sectional view of a p-n diode layer formed on a patterned substrate and including orientation dependent doping in accordance with an embodiment.
  • the method illustrated in FIGS. 11A-11D is directed toward phosphorus based LEDs designed for emission of red light.
  • a growth substrate 1002, such as (100) GaAs substrate is formed with etched steps 1101.
  • a p-n diode layer 1115 is then epitaxially grown on the patterned growth substrate 1002.
  • the p-n diode layer includes n-AlInP current spreading layer 104, n-AlInGaP:Se or Si cladding layer 106, InGaP active layer 108, p-AlInGaP:Mg cladding layer 1110A, co-doped AlGaInP:Mg+Se cladding layer 1110B, p-AlInGaP:Mg cladding layer 1110C, and p-GaP current spreading layer 112.
  • the particular method of forming the cladding layers 1110A-C, and particularly cladding layer 1110B implements orientation-dependence of n, p doping within the cladding layer 1110B.
  • an n-type cladding layer 1110B is formed on the (100) planar surfaces, and a net p-type cladding layer 1110B is formed along the sloped regions.
  • Se is incorporated within the AlGaInP cladding layer 1110B at (100) orientation
  • Mg is preferentially incorporated within the AlGaInP cladding layer 1110B along the misoriented slope resulting in p-n diode layer 1115 in which the p-n junction is located on the sloped sidewalls, while n-p-n-p junctions are formed on the (100) surface.
  • the current injection path preferentially (illustrated as an arrow in FIG. 11A ) flows through the p-n junction formed on the sloped sidewalls.
  • FIGS. 11B-11D the processing sequence is similar to that described above with regard to FIGS. 1B-1F to form LEDs 1150.
  • FIGS. 11E-11F are cross-sectional side view illustrations of LED p-n junctions with orientation dependent doping in accordance with example not forming part of the invention.
  • the p-n junction, and current injection paths are located internally within the LED 1150 away from the active layer 108 edges along sidewalls 153 of the p-n diode layer.
  • a portion of the growth substrate 102 is left behind within the resultant LED 1150.
  • thickness of the p-n diode layer 1115 is sufficient enough to fill the internal portion of the LED 1150.
  • current spreading layer 104 may fill the interior portion of the LED 1150.
  • FIGS. 12A-12F are cross-sectional side view illustrations of a method of forming an LED with selective etching and mass transport in accordance with an example not forming part of the invention.
  • a p-n diode layer 115 is formed on a growth substrate 102, similarly as described above with regard to FIG. 1A .
  • the p-n diode layer 115 may be designed for red, green, or blue emission. Though, the particular processing sequence may depend upon whether the p-n diode layer 115 nitride based or phosphorus based.
  • trenches 118 are formed through the p-n diode layer 115 to form mesa structures 120 as previously described.
  • the p-n diode layer 115 is phosphorus based, and a selective etch of an InGaP active layer 108 is performed to create a notch in the active layer as illustrated in FIG. 12C .
  • the p-n diode layer 115 is nitride based, and a light activated (e.g. between 365 and 450 nm) photo-electrochemical etch selectively removes a portion of an InGaN active layer 108 to produce a notch.
  • a light activated e.g. between 365 and 450 nm
  • mass-transport at high temperatures causes mass-transport of the adjacent materials to form a new p-n junction that envelops the notched active layer 108. It is contemplated that mass-transport may possibly envelop the edges of the active layer 108 without first forming a notch.
  • mass transport is caused by exposure to PH 3 + H 2 at high temperature.
  • the adjacent p-AlInGaP cladding layer 110 and n-AlInGaP cladding layer 106 envelope the InGaP active layer 108.
  • the p-n diode layer 115 is nitride based
  • mass transport is caused by exposure to NH 3 + H 2 at high temperature.
  • the adjacent p-GaN current spreading layer 112 and n-GaN current spreading layer 104 envelope the InGaN active layer 108.
  • the structure may then be processed similarly as described above with regard to FIGS. 1B-1F to form LEDs 1250.
  • FIGS. 12G-12H are cross-sectional side view illustrations of LEDs including a notched active layer in accordance with an example not forming part of the invention.
  • the adjacent p-AlInGaP cladding layer 110 and n-AlInGaP cladding layer 106 envelope the InGaP active layer 108.
  • the adjacent p-GaN current spreading layer 112 and n-GaN current spreading layer 104 envelope the InGaN active layer 108.
  • the edges 151 of the active layer 108 are internally confined within the LED 1250, inside of the p-n diode layer sidewalls 153.
  • FIGS. 13A-13C are cross-sectional side view illustrations of a method of passivating the sidewalls of an LED with surface conversion in accordance with an example not forming part of the invention.
  • FIGS. 13A-13B are substantially similar to FIGS. 12A-12B for a phosphorus based p-n diode structure, with a slight difference in composition.
  • the active layer 108, and optionally the cladding layers 106, 110 include arsenic in their alloys.
  • aluminum may additionally be included in the layers 106, 108, 110 to restore the bandgap value.
  • the mesa structures 120 are exposed to PH 3 + H 2 vapor at high temperature, which results in incongruent sublimation in which the group V species evaporate. The escaping As species is replaced by P, and the surface bandgap energy is raised. As a result, the edges 151 of the active layer 108 become internally confined within the LED, inside of the p-n diode layer sidewalls 153.
  • FIG. 14A is cross-sectional side view illustration of an LED with quantum dots in the active layer in accordance with an example not forming part of the invention.
  • the structure illustrated in FIG. 14A is directed toward phosphorus based LEDs designed for emission of red light.
  • an LED 1450 includes a quantum dot active region 1408 in which injected carriers are localized at the quantum dots and less likely to diffuse to the LED sidewalls 151.
  • FIG. 14B is schematic top view illustration of an LED active layer with quantum dots 1409 in accordance with an embodiment.
  • cladding layer 1410 is formed of p-AlInP
  • cladding layer 1406 is formed of n-AlInP
  • active layer 108 is formed of (Al)GaInP.
  • deposition is controlled such that compressive strain causes segregation of In into In-rich areas.
  • Deposition conditions can also be controlled to take advantage of the miscibility gap to form In-rich areas.
  • the In-rich quantum dot clumps with lower band gaps, trap the carriers and suppress lateral diffusion to the LED sidewalls 151.
  • Detection of the quantum dot clumps in the non-homogenous active layer 108 may be detected by, for example, photoluminescence.
  • quantum dot clumps 1409 depends upon the lens scale over which low band gap regions are formed, and may be on the order of 10-20 nm in an embodiment.
  • FIGS. 15A-15C are cross-sectional side view illustrations of a method of forming an LED with nanopillars in the active layer in accordance with an example not forming part of the invention.
  • the structure illustrated in FIG. 15A is directed toward nitride based LEDs designed for emission of green or blue light.
  • p-n diode layer 1515 includes a n-GaN current spreading layer 104, p-AlGaN cladding layer 110, and p-GaN current spreading layer 112. Multiple layers may form the active layer.
  • multiple active layers include InGaN.
  • a first In 1 GaN active layer 1508A includes a plurality of nanopillars 1509.
  • the nanopillars 1509 can be formed spontaneously by compressive strain in the In 1 GaN active layer 1508A.
  • the nanopillars 1509 are formed by selective growth, or patterning.
  • a second In 2 GaN active layer 1508B is formed with higher indium content than in the first In 1 GaN active layer 1508A.
  • a larger concentration of indium may be located on the quantum dots, or nanopillars 1509.
  • the indium segregation may additionally increase the size of the nanopillars 1509.
  • third In 3 GaN active layer 1508C is grown over and buries the quantum dots, or nanopillars 1509.
  • the indium content in In 3 GaN active layer 1508C is less than the indium content in In 2 GaN active layer 1508B, and may be the same as with In 1 GaN active layer 1508A.
  • the structure may be processed similarly as described above with regard to FIGS. 1B-1F to form LEDs 1550.
  • FIG. 15D is cross-sectional side view illustration of an LED with nanopillars in the active layer in accordance with an embodiment.
  • FIG. 15E is cross-sectional side view illustration of an LED with nanopillars in the active layer and a top hat configuration in accordance with an embodiment. As illustrated the bottom p-doped current spreading layer 112 is formed in a pillar formation.
  • the LEDs 1550 include quantum dots, or nanopillars 1509 within the active region 1508 in which injected carriers are localized at and less likely to diffuse to the LED sidewalls 151, which also correspond to the p-n diode layer sidewalls 153.
  • FIGS. 16A-16D are cross-sectional side view illustrations of a method of forming an LED with heterostructure intermixing at the p-n diode layer sidewalls in accordance with an example not forming part of the invention.
  • the structure illustrated in FIG. 16A is directed toward phosphorus based LEDs designed for emission of red light, and may include a p-n diode layer 115 similar as with described above with regard to FIG. 1A .
  • injection masks 1601 are formed over the current spreading layer 112. A thermal operation is then performed to cause diffusion or intermixing, depending upon the material of the injection masks 1601.
  • the injection masks 1601 are formed of silicon.
  • silicon diffuses from the surface to form an intermixed region 1602. Diffusion of silicon causes group III vacancies, which enable group III atoms (Al, Ga, In) to exchange lattice positions on the group III sublattice to form a homogeneous alloy across layers 106 (originally AlInGaP), 108 (originally InGaP), 110 (originally AlGaInP). Still referring to FIG. 16B , after silicon diffusion, a blanket Zn-donor layer is optionally formed over current spreading layer 112 and diffused into the surface to form p-doped layer 1603 across the surface, particularly where silicon (n-dopant) was diffused.
  • group III atoms Al, Ga, In
  • FIGS. 16C-16D trenches 118 are etched through the p-n diode layer 115 and the structure is patterned similarly as described above with regard to FIGS. 1B-11F to form LEDs 1650.
  • FIG. 16E is cross-sectional side view illustration of an intermixed LED heterostructure in accordance with an embodiment. As shown the intermixed regions 1602 are formed adjacent the active layer 108 such that the edges 151 of the active layer 108 are internally confined within the p-n diode layer sidewalls 153.
  • the injection masks 1601 are formed of SiO 2 , which inject group III vacancies into the underlying material.
  • Al, Ga, In diffuse into the SiO 2 to form the intermixed region 1602 were Al, Ga, and In are intermixed.
  • injection masks 1601 are formed of SiO 2 , and Si doping layers 1611 are formed in the vicinity of the one or more active layers 108.
  • the Si doping layers 1611 may function to accelerate the intermixing in the vicinity of the active layers 108.
  • the array of LEDs may then be transferred from the carrier substrate to a receiving substrate, such as a lighting or display substrate.
  • the transfer may be accomplished by selective removal of the sacrificial release layer, for example by vapor HF etch followed by electrostatic transfer of the array of LEDs using a transfer tool including an array of electrostatic transfer heads.
  • FIGS. 17A-17F are cross-sectional side view illustrations of a method of forming an LED with a sidewall passivation layer in accordance with an example not forming part of the invention.
  • a bulk LED substrate 100 is illustrated, similarly as previously described above with regard to FIG. 1A .
  • a conductive oxide layer 160 such as ITO, may be formed over the p-n diode layer 115.
  • the conductive oxide layer 160 may make ohmic contact with a current spreading layer (e.g. 112) or cladding layer (e.g. 110) of the p-n diode layer 115.
  • the conductive oxide layer 160 and p-n diode layer 115 may then be patterned to form trenches 118, as illustrated in FIG. 17B .
  • the substrate may be conditioned. For example, this may include an acid dip to remove native oxide or residual contamination in an HCl or bromine based mixture. Then an in-situ plasma treatment may optionally be performed, for example using argon, hydrogen, or nitrogen.
  • a sidewall passivation layer 170 is formed over and between the mesa structures 120.
  • sidewall passivation layer 170 is formed using atomic layer deposition (ALD),
  • ALD atomic layer deposition
  • sidewall passivation layer may 170 be Al 2 O 3 , though other materials may be used.
  • sidewall passivation layer 170 is between 0 - 1,000 nm thick, such as 1 - 100 nm thick, and may have a uniform thickness that conforms the underlying substrate topography, and forms an outline around the mesa structures 120.
  • the sidewall passivation layer 170 may then be patterned to form openings 170 over the mesa structures 120 that expose the patterned conductive oxide layer 160. For example, this may be accomplished using a fluorine based dry etching technique.
  • Bottom conductive contacts 116 may then be formed on the exposed portions of conductive oxide layers 160 within openings 172 as illustrated in FIG. 17D .
  • a patterned sacrificial oxide layer 122 is formed, and the patterned structure is bonded to a carrier substrate 140 with an adhesive bonding material to form stabilization layer 130.
  • the growth substrate 102 may be removed utilizing a suitable technique such as laser lift-off, etching, or grinding to expose the p-n diode layer 115. Any remaining portions of the p-n diode layer 115 connecting the separate mesa structures 120 may then be removed using etching or grinding to form laterally separate p-n diode layers 115.
  • a top conductive contact layer 142 may then be formed over each laterally separate p-n diode layer resulting LEDs 150 as illustrated in FIG. 17F .
  • the ALD sidewall passivation layer 170 spans along the p-n diode layer 115 sidewalls 153 (e.g. including the top current spreading layer 104, the active layer 108, and the bottom current spreading layer 112), as well as underneath the conductive oxide layer 160.
  • FIGS. 18A-18D are cross-sectional side view illustrations of a method of forming an LED with heterostructure intermixing at the p-n diode layer sidewalls in accordance with an embodiment of the present invention. Specifically, FIGS. 18A-18D illustrate a top-down diffusion method.
  • a bulk LED substrate 100 is illustrated, similarly as previously described above with regard to FIG. 1A , with exemplary quantum well 107 and quantum barrier layers 109 illustrated within the active layer 108.
  • a single quantum well layer 107 is illustrated, in accordance with the present invention a multiple quantum well layer structure is used.
  • the bulk LED substrate 100 structure may be applicable to a variety of compositions and designed emission spectra.
  • the bulk LED substrate 100 may include II-VI materials, III-V nitride materials, or III-V phosphide materials and be designed for emission of a variety of emission spectra.
  • the bulk LED substrate 100 may fabricated with an AlInGaP material system or ZnMgBeSSe material system.
  • the bulk LED substrate 100 is based on an AlInGaP material system and is designed for red color emission.
  • bulk LED substrate 100 may be designed for a peak emission wavelength between 600 nm -750 nm, such as 620 nm.
  • the exemplary structures may be used for LEDs based on different material systems.
  • formation of the bulk LED substrate begins with the formation of a device layer 115 on a growth substrate 102, such as a GaAs growth substrate, for example with a thickness of 250 - 1,000 ⁇ m.
  • Growth substrate 102 may optionally be doped, for example with an n-type dopant such as silicon (Si) or tellurium (Te).
  • Layers 104-112 of the device layer 115 may then be grown on the growth substrate 102 using a suitable technique such as metal organic chemical vapor deposition (MOCVD).
  • MOCVD metal organic chemical vapor deposition
  • An n-type current spreading layer 104 is grown over the growth substrate 102, for example to a thickness of 0.05 - 0.5 ⁇ m.
  • N-type current spreading layer 104 may be formed of materials such as AlInP, AlGaInP, and AlGaAs. In an embodiment, n-type current spreading layer 104 is formed of AlInP with a Si dopant concentration of 1 ⁇ 10 18 cm -3 . An n-side (top) cladding layer 106 is then grown on the n-type current spreading layer 104, for example to a thickness of 0.05 - 0.5 ⁇ m. N-side cladding layer 106 may be formed of materials such as AlInP, AlGaInP, and AlGaAs, and may or may not be doped. In an embodiment, n-side cladding layer 106 is formed of AlInGaP, and is unintentionally doped during growth.
  • the n-side cladding layer 106 does not have a graded composition (e.g. Aluminum content is uniform).
  • An active region 108 is then grown on the n-side cladding layer 106.
  • Active region 108 may include one or more quantum well (QW) layers 107 and quantum barrier layers 109, which may be formed of the same alloy system (e.g. AlInGaP system) as the surrounding cladding layers 106, 110.
  • QW quantum well
  • a p-side (bottom) cladding layer 110 is then optionally grown on the active layer 108, for example to a thickness of 0.05 - 0.5 ⁇ m, or more specifically approximately 100 nm.
  • P-side cladding layer 110 may be formed of materials such as AlInP, AlGaInP, and AlGaAs, and may or may not be doped.
  • p-side cladding layer 110 is formed of AlInGaP, and is unintentionally doped during growth.
  • a p-type (bottom) current spreading layer 112 may then be formed on the p-side cladding layer 110.
  • the p-type current spreading layer 112 may be formed of materials such as AlInP, AlGaInP, and AlGaAs.
  • p-type current spreading layer 112 is formed of AlInP with a Mg dopant concentration of 5 ⁇ 10 17 cm -3 - 1.5 ⁇ 10 18 cm -3 .
  • the p -type current spreading layer 112 may have a substantially uniform p-dopant concentration, less a concentration gradient due to diffusion with the surrounding layers. In an embodiment, the p-dopant concentration is not uniform.
  • the cladding layers 106, 110 may be formed of a material with a large conduction band offset with respect to the one or more quantum well layers 107 in the active layer 108.
  • a maximum conduction band offset to the quantum wells confines electrons to the quantum wells.
  • the doped current spreading layers 104, 112 may be selected to have a high band gap in order to confine the injected carriers.
  • the doped current spreading layers 104, 112 may have a higher bandgap energy than the adjacent cladding layers.
  • the cladding layers 106, 110 are (Al x Ga 1-x ) 0.5 In 0.5 P alloys with 0.2 ⁇ x ⁇ 0.8, such as 0.5 ⁇ x ⁇ 0.8.
  • the doped current spreading layers 104, 112 are (Al x Ga 1-x ) 0.5 In 0.5 P alloys with 0.6 ⁇ x ⁇ 1.0.
  • Dopant wells 1801 are then formed in the bulk LED substrate as illustrated in FIG. 18B .
  • the dopant wells extend through the one or more quantum wells 107 and quantum barrier layers 109 within the active layer 108.
  • Dopant wells 1801 may be formed using techniques such as implantation, solid source diffusion, or vapor diffusion.
  • dopant wells 1801 are p-type, and include a dopant profile of a dopant such as Zn or Mg, or more specifically Zn.
  • current spreading layer 112, and optionally cladding layer 110 are p-doped with a p-dopant such as Zn or Mg, or more specifically Mg during growth of the p-n diode layer 115.
  • a p-dopant such as Zn or Mg, or more specifically Mg during growth of the p-n diode layer 115.
  • In-situ doping with Mg may be selected due to a corresponding low activation energy, and the ability to create free holes, while Zn may be selected for the formation of dopant wells 1801 due to a greater ability to diffuse.
  • An array of mesa trenches 118 may then be formed in the device layer to form an array of mesa structures 1820 in accordance with embodiments.
  • the mesa trenches 118 may be formed through the dopant wells 1801, resulting in doped confinement regions along sidewalls 153 of the mesa structures 1820.
  • the patterned bulk LED substrates may be processed similarly as described above to form an array of LEDs 1850 that are poised for pick up and transfer to a receiving substrate.
  • FIG. 18E-18F are cross-sectional side view illustrations of intermixed LED heterostructures in accordance with an embodiment of the present invention.
  • the intermixed regions 1802 are formed adjacent the active layer 108 such that the edges 151 of the active layer 108 are internally confined within the p-n diode layer sidewalls 153.
  • the intermixed regions 1802 are formed within the original quantum well layer(s) 107 and quantum barrier layers 109 forming the original active layer 108 where the diffusion profile of the dopant wells 1801 overlap the active layer 108.
  • the intermixed regions 1802 may be characterized by a larger bandgap than the original quantum well layers 107 due to diffusion between the quantum well layers 107 and quantum barrier layers 109, and resultant alloy intermixing.
  • intermixing may result in the transformation of multiple quantum well layers 107 and quantum barrier layers 109 to form a singular intermixed region 1802 with a larger bandgap than the original quantum well layers 107.
  • dopants e.g.
  • the dopants from dopant wells 1801 may facilitate alloy intermixing within the intermixed regions 1802, which may raise the bandgap of the intermixed regions 1802 relative to the quantum well layers 107 confined inside of the LED interior to the intermixed regions 1802. As described in further detail below, diffusion and alloy intermixing may be further facilitated by controlling layer thickness, composition difference, and strain.
  • the LEDs 1850 are micro LEDs, with a maximum width between sidewalls 153 of 1-300 ⁇ m, 1-100 ⁇ m, or more specifically 1-20 ⁇ m, such as 10 ⁇ m or 5 ⁇ m where the micro LED lateral dimensions may approach the carrier diffusion length.
  • the edges 151 of the active layer 108 are internally confined at least 200 nm within the p-n diode layer sidewalls 153.
  • the intermixed regions 1802 may be at least 200 nm wide.
  • FIGS. 19A-19D are cross-sectional side view illustrations of a method of forming an LED with heterostructure intermixing at the p-n diode layer sidewalls in accordance with an embodiment of the present invention. Specifically, FIGS. 19A-19D illustrate a sidewall diffusion method similar to FIGS. 6A-6F . As illustrated in FIG. 19A , a bulk LED substrate 100 is illustrated, similarly as previously described above with regard to FIG. 1A and FIG. 18A , with exemplary quantum well layer 107 and quantum barrier layers 109 illustrated within the active layer 108.
  • an array of mesa trenches 118 is formed in the device layer to form an array of mesa structures 1920 in accordance with embodiments.
  • trenches 118 may be formed through the confinement layer 106, and partially or completely through the current spreading layer 104. Etching may be performed using suitable wet etching or dry etching techniques, or a combination thereof such as dry etching followed by final wet etching to remove physical sidewall damage caused by dry etching.
  • Mask layers 1910 may be used to pattern the mesa structures 1920.
  • dopants are implanted or diffused into exposed surfaces of the array of mesa structures 1950 and the device layer 115 laterally between the adjacent mesa structures.
  • Doped regions 1901 may be n-type or p-type.
  • doped regions 1901 are p-type, such as Mg or Zn.
  • the p-type dopant is an element that produces a high doping concentration and relatively low mobility, such as Mg.
  • the patterned bulk LED substrates may be processed similarly as described above to form an array of LEDs 1950 that are poised for pick up and transfer to a receiving substrate.
  • FIGS. 19E-19F are cross-sectional side view illustrations of intermixed LED heterostructures in accordance with an embodiment of the present invention.
  • the intermixed regions 1902 are formed adjacent the active layer 108 such that the edges 151 of the active layer 108 are internally confined within the p-n diode layer sidewalls 153.
  • the intermixed regions 1902 are formed within the original quantum well layers 107 and quantum barrier layers 109 forming the original active layer 108 where the diffusion profile of the doped region 1901 overlap the active layer 108.
  • the intermixed regions 1902 may be characterized by a larger bandgap than the original quantum well layers 107 due to diffusion between the quantum well layers 107 and quantum barrier layers 109, and resultant alloy intermixing.
  • intermixing may result in the transformation of multiple quantum well layers 107 and quantum barrier layers 109 to form a singular intermixed region 1902 with a larger bandgap than the original quantum well layers 107.
  • dopants e.g.
  • Mg from the doped region 1901 may facilitate diffusion from the original quantum barrier layer 109 into the quantum well layer 107 to form intermixed regions 1902, and/or diffusion of In from the quantum well layers 107 into the quantum barrier layers 109 to form intermixed regions 1902.
  • the dopants from doped region 1901 may facilitate alloy intermixing within the intermixed regions 1902, which may raise the bandgap of the intermixed regions 1902 relative to the quantum well layers 107 confined inside of the LED interior to the intermixed regions 1902.
  • diffusion and alloy intermixing may be further facilitated by controlling layer thickness, composition difference, and strain.
  • the LEDs 1950 are micro LEDs, with a maximum width between sidewalls 153 of 1-300 ⁇ m, 1-100 ⁇ m, or more specifically 1-20 ⁇ m, such as 10 ⁇ m or 5 ⁇ m where the micro LED lateral dimensions may approach the carrier diffusion length.
  • the edges 151 of the active layer 108 are internally confined at least 200 nm within the p-n diode layer sidewalls 153.
  • the intermixed regions 1902 may be at least 200 nm wide.
  • LED may include a p-n diode layer including a top doped layer (e.g. 104, or 106) that is doped with a first dopant type (e.g. n-type), a bottom doped layer (e.g. 1120, or 110) doped with a second dopant type (e.g. p-type) that is opposite the first type, though the doping types may be transposed.
  • An active layer 108 is between the top doped layer and the bottom doped layer, and p-n diode layer sidewalls 153 span the top doped layer, the active layer 108, and the bottom doped layer.
  • An intermixed region e.g.
  • the active layer 108 includes a plurality of quantum well layers 107 and a plurality of quantum barrier layers 109.
  • the intermixed region (e.g. 1802, 1902, etc.) may have a higher bandgap than each of the plurality of quantum well layers 107. For example, this may be attributed to the intermixed region (e.g. 1802, 1902, etc.) having a higher concentration of Al than each of the plurality of quantum well layers 107, and/or the intermixed region (e.g. 1802, 1902, etc.) having a lower concentration of In than each of the plurality of quantum well layers 107.
  • the original as-grown quantum well layers 107 after intermixing become interior quantum well layers 107 and portions of the surrounding intermixed regions (e.g. 1802, 1902, etc.), and while the overall Al content in the system is preserved, the intermixed regions (corresponding to a transformed portion of the original as-grown quantum well layers) include more Al than the remaining interior quantum well layers 107.
  • the bottom doped layer is in-situ doped with a dopant (e.g. Mg) of the second dopant type (e.g. p-type).
  • the LED may additionally include a profile of a second dopant (e.g.
  • a Zn doping profile is the result of a top down diffusion method
  • a Mg doping profile is the result of a sidewall diffusion method, though embodiments are not so limited.
  • intermixing within the intermixed regions may be facilitated by active layer 108 design, for example, by controlling layer thickness, composition, and strain of the formational layers.
  • active layer 108 design for example, by controlling layer thickness, composition, and strain of the formational layers.
  • various embodiments are described which may facilitate intermixing. Each embodiment is described relative to a baseline active layer structure including 8 nm thick (Al 0.1 Ga 0.9 ) 0.5 In 0.5 P quantum well layers 107 and 10 nm thick (Al 0.7 Ga 0.3 ) 0.5 In 0.5 P quantum barrier layers 109, in a structure designed for emission at approximately 620 nm.
  • the Al concentration of 0.7 may represent the value in which a maximum conduction-valence band offset is accomplished for the quantum barrier layer 109. It is to be appreciated, however, that the following embodiments may also be applicable to alterative structures designed for emission at different wavelengths.
  • a thickness of the one or more quantum well layers 107 is reduced in order to facilitate intermixing.
  • a thinner quantum well layer 107 may undergo a larger energy shift for a given intermixing distance.
  • a thinner quantum well layer 107 may additionally allow for a lower dopant concentration in the dopant wells 1801, doped regions 1901.
  • the quantum well layer(s) 107 are thinner than each of the quantum barrier layers 109.
  • the quantum well layer(s) 107 each have a thickness between 2-8 nm, or more specifically 2-5 nm, such as 4 nm.
  • the composition of the constituent layers of the active layer 108 are selected to facilitate intermixing.
  • the composition selection may additionally be combined with the quantum well layer 107 thickness reduction.
  • the material system for the quantum barrier layers 109 and active layers 107 is (Al x Ga (1-x) ) y In (1-y) P.
  • increasing the Al content difference between the quantum barrier layers 109 and active layers 107 may facilitate Al diffusion, and intermixing.
  • a ⁇ x between the quantum barrier layers 109 and active layers 107 may be greater than 0.6, or greater than 0.8.
  • Al concentration in the quantum barrier layers 109 is increased.
  • the quantum well layer(s) 107 may be reduced.
  • Sb may be substituted completely or partially for P.
  • reducing or removing Al increases Ga concentration, while adding As lowers P concentration, the effect of both being to reduce the band gap.
  • the quantum well layers 107 are compressively strained.
  • a lattice mismatch between 0-2% may be created between the quantum well layers 107 and adjacent quantum barrier layers 109.
  • strain may be at least partially controlled by composition.
  • increasing In concentration may increase the lattice parameter of the quantum well layers 107.
  • quantum barrier layers 109 have a baseline composition of thick (Al 0.7 Ga 0.3 ) 0.5 In 0.5 P, and may be 8 nm thick, for example.
  • the indium concentration in the baseline quantum well layers 107 may be increased to (Al 0.2 Ga 0.8 ) 0.4 In 0.6 P, which results in an increased lattice size, and the quantum barrier layers 109 putting the quantum well layers 107 under compression.
  • In diffusion may play a role in the intermixed regions 1802 and 1902, in which In from the active layers 107 diffuses into the quantum barrier layers 109, which has the effect of raising the band gap in the intermixed regions 1802 and 1902. This may additionally have the effect of allowing a lower Al concentration difference between the quantum well layers 107 and quantum barrier layers 109.
  • quantum well layers 107 and quantum barrier layers 109 may be strain balanced.
  • the quantum well layers 107 are under compressive strain, while the quantum barrier layers 109 may be under tensile strain.
  • the net thickness of the active layer 108 is strain balanced.
  • a strain balanced active layer 108 may include a larger Al concentration difference and In concentration difference, compared to the baseline composition.
  • the In concentration difference may be greater than 0.1, such as 0.2.
  • a strain balanced active layer 108 includes (Al 0.2 Ga 0.8 ) 0.4 In 0.6 P active layers 107 and (Al 0.7 Ga 0.3 ) 0.6 In 0.4 P quantum barrier layers 109.
  • an increased In concentration in the active layers 107 may increase the lattice size, while a decreased In concentration in the quantum barrier layers 109 may decrease lattice size.
  • the larger lattice active layers 107 may place the quantum barrier layers 109 under tension, and the smaller lattice size quantum barrier layers 109 may place the active layers 107 under compressive strain.
  • FIG. 20 is an in-plane band structure for unstrained, compressively strained, and tensile strained GaInP quantum well layer materials.
  • energy (E) is plotted versus momentum (k), for electrons (e), light holes (lh) and heavy holes (hh) for unstrained Ga 0.5 In 0.5 P, compressively strained, indium rich, Ga 0.4 In 0.6 P, and tensile-strained, indium deficient, Ga 0.6 In 0.4 P.
  • the light hole (lh) valence band is the ground state, and is relatively flat, which corresponds to a high effective mass. It is believed the high effective mass for holes in the case of tensile-strained quantum wells translates to low hole mobility, and correspondingly to reduced diffusion toward the LED sidewalls.
  • FIG. 21 is cross-sectional side view illustration of an LED 2150 heterostructure with a tensile strained and modulation-doped quantum well active region in accordance with an example not forming part of the invention.
  • the LED heterostructure may include a current spreading layer 104 of a first dopant type (e.g. n-doped), a current spreading layer 112 of opposite dopant type (e.g. p-doped), and an active layer 108 between the current spreading layers 104, 112.
  • Cladding layers 106, 110 may optionally be formed on opposite sides of the active layer 108 to confine current within the active layer 108 and may possess a larger bandgap than the active layer 108.
  • Cladding layers 106, 110 may be doped to match the doping of the adjacent current spreading layers 104, 112.
  • cladding layer 106 is doped with an n-type dopant
  • cladding layer 110 is doped with a p-type dopant, or vice versa.
  • the current spreading layers may be functionally similar to cladding layers.
  • the LED heterostructure is designed for emission of red light, and the materials are phosphorus based.
  • the layers forming the p-n diode may include AlInP, AlInGaP, AlGaAs, GaP, and GaAs.
  • current spreading layer 104 includes n-AlInP or n-AlGaInP
  • cladding layer 106 includes AlInGaP
  • cladding layer 110 includes AlGaInP
  • current spreading layer 112 includes p-GaP or p-AlInP.
  • Quantum well 108 may be formed of a variety of materials, such as but not limited to, AlGaInP, AlGaAs, and InGaP.
  • the active layer 108 includes multiple quantum well layers 107 and quantum barrier layers 109.
  • the quantum barrier layers 109 are formed of the same material system as the cladding layers 106, 110.
  • the quantum barrier layers 109 may be formed of AlInGaP, such as (Al 0.7 Ga 0.3 ) 0.5 In 0.5 P.
  • the quantum barrier layers 109 may be modulation doped, for example, n-doped with a suitable n-type dopant such as Si.
  • an exemplary doping concentration may be 1 ⁇ 10 17 cm -3 - 1 ⁇ 10 18 cm -3 .
  • the quantum well layer 107 may be strained, such as tensilely-strained as described with regard to FIG. 20 .
  • the quantum well layers 107 are formed of InGaAlP, with a reduced indium concentration.
  • quantum well layers 107 may be In x (Ga y Al 1-y ) 1-x P (x ⁇ 0.5, y>0.9), such as Ga 0.6 In 0.4 P.
  • x ⁇ 0.5 corresponds to a reduced indium concentration, in which a lower limit on reduction of indium concentration may be bound by a critical thickness of the layer.
  • n-type modulation doping of the quantum barrier layers 109 produces a high concentration of majority electrons in the quantum well layers 107. These electrons are available for recombination with injected holes, increasing the radiative rate relative to an undoped quantum well layer 107. In the presence of majority electrons, radiative recombination is favored and the carrier diffusion is limited by the hole transport. Where the quantum well layers 107 are tensilely strained, the holes are rendered less mobile by the tensile strain, and are less likely to diffuse to the sidewall. As a result, the carrier diffusion length is reduced, and corresponding non-radiative sidewall recombination is also reduced.
  • both n-type modulation and tensile strained quantum well layers reduce non-radiative sidewall combination, alone and in combination.
  • these designs may be used together, as well as with other sidewall treatments described herein for reduced non-radiative sidewall combination.
  • FIG. 22 is a cross-sectional side view illustration of an LED with a current spreading layer pillar structure with a reduced width compared to the active layer in accordance with an example not forming part of the invention.
  • the LED heterostructure may include a current spreading layer 104 of a first dopant type (e.g. n-doped), a current spreading layer 112 of opposite dopant type (e.g. p-doped), and an active layer 108 between the current spreading layers 104, 112.
  • Cladding layers 106, 110 may optionally be formed on opposite sides of the active layer 108 to confine current within the active layer 108 and may possess a larger bandgap than the active layer 108.
  • Cladding layers 106, 110 may be doped to match the doping of the adjacent current spreading layers 104, 112.
  • cladding layer 106 is doped with an n-type dopant
  • cladding layer 110 is doped with a p-type dopant, or vice versa.
  • the LED heterostructure is designed for emission of blue or green light, and the materials are nitride based.
  • the following listing of materials for blue or green emission is intended to be exemplary and not limiting.
  • the layers forming the p-n diode may include GaN, AlGaN, InGaN.
  • current spreading layer 104 includes n-GaN
  • cladding layer 106 includes n-InGaN
  • cladding layer 110 includes p-AlGaN (e.g. Mg dopant)
  • current spreading layer 112 includes p-GaN.
  • Quantum well 108 may be formed of a variety of materials, such as but not limited to, InGaN.
  • the active layer 108 includes multiple quantum well layers 107 and quantum barrier layers 109.
  • the quantum barrier layers 109 are formed of undoped GaN
  • the quantum well layers are formed of InGaN.
  • the LED may include a centrally located pillar structure 220 with a reduced width compared to the active layer 108.
  • the LED may optionally include a double mesa structure including the pillar structure 220 extending from a mesa 222, which extends from the current spreading layer 104.
  • the pillar structure 220 may include the current spreading layer 112 and cladding layer 110.
  • the pillar structure 220 may extend completely through the cladding layer 110, as illustrated, or partially through the cladding layer 110.
  • the pillar structure 220 may circumvent non-radiative recombination along sidewalls 253 of the LED laterally adjacent the active layer 108, for example, along the mesa structure 222.
  • the pillar structure 220 and mesa structure 222 may be formed utilizing a suitable etching technique such as dry etching.
  • a suitable etching technique such as dry etching.
  • FIG. 23 a cross-sectional side view illustration is provided of an LED with a current spreading layer pillar structure 220 and a set-back spacer layer 232 in accordance with an embodiment. It has been observed that dry etching may be accompanied by the creation of defects underneath the etched surfaces, such as surface 221 of the mesa structure 222 over the quantum well layers 107. Propagation of such defects into the quantum well layers 107 may adversely affect device performance.
  • Mg doping within cladding layer 110 experiences a surface riding effect due to growth conditions of the cladding layer 110 during MOCVD, in which the Mg doping concentration is largest at the top growth surface, which corresponds to the surface adjacent the current spreading layer 112.
  • Mg doping concentration within a p-AlGaN cladding layer 110 is highest adjacent the p-GaN current spreading layer 112 interface.
  • This Mg doping concentration within the cladding layer 110 may also have an important relationship to injection efficiency of the LED. Accordingly, Mg dopant concentration and proximity to the quantum well layers 107 may be strictly controlled parameters for device performance.
  • an LED structure is illustrated that bifurcates the cladding layer 110 with a spacer layer 232, so that a first cladding layer 110A can be formed to a thickness sufficient to absorb defects due to dry etching of the pillar structure 220, while the second cladding layer 110B can be thin enough to keep the Mg doping concentration close to the quantum well layers 107, despite the observed surface riding effect. Additionally, the thickness of the first and second cladding layers 110A, 110B can each be maintained below a critical thickness to avoid cracking of the epitaxial films.
  • the first cladding layer 110A is relatively thick, such as greater than 10 nm thick, or even greater than 50 nm thick such as 50 to 100 nm thick.
  • first cladding layer 110A may be formed of AlGaN, with an Al composition of approximately 10%, and lightly doped with Mg (e.g. 1 ⁇ 10 19 cm -3 ).
  • the first cladding layer 110A may additionally function as an etch stop/end signal layer during etching of the pillar structure 220, in addition to providing a set-back distance for defects.
  • the spacer layer 232 is thin, and lightly doped.
  • the spacer layer 232 may be approximately 5 nm thick, to mitigate current spreading within the layer, and lightly doped to mitigate conductivity.
  • the spacer layer 232 may be formed of p-GaN.
  • the second cladding layer 110B (which corresponds to the first grown cladding layer on the bulk LED substrate) can be relatively thinner, and more heavily doped than the first cladding layer 110A.
  • the second cladding layer 110B may be less than 50 nm thick, such as 5 to 10 nm thick, with a peak Mg doping concentration of at least 1 ⁇ 10 19 cm -3 .
  • the second cladding layer 110B may be formed of p-AlGaN. In such a configuration, the spacer layer 232 may break the Mg surface riding effect, and function to keep the peak Mg doping concentration within the second cladding layer 110B near the quantum well layers 107.
  • the second cladding layer 110B may additionally function as an electron blocking layer.
  • a sidewall passivation layer 170 may optionally be formed along the exposed sidewalls.
  • sidewall passivation layer may 170 be Al 2 O 3 , though other materials may be used.
  • the LEDs of FIGS. 22-23 may include top conductive contacts 142 formed on the current spreading layers 104, and bottom conductive contacts formed on the current spreading layers 112. Additionally, the LED structures of FIGS. 22-23 may be combined other sidewall treatments described herein for reduced non-radiative sidewall combination.
  • a maximum lateral dimension between the sidewalls of the LEDs of FIGS. 22-23 is 1 to 300 ⁇ m, or more specifically 1 to 100 ⁇ m, 1 to 30 ⁇ m, 1 to 10 ⁇ m, or 1 to 5 ⁇ m.
  • a maximum lateral dimension between sidewalls 253 of the mesa structures 222 may be 1 to 300 ⁇ m, or more specifically 1 to 100 ⁇ m, 1 to 30 ⁇ m, 1 to 10 ⁇ m, or 1 to 5 ⁇ m.
  • a difference in width of the pillar structure 220 where it meets the mesa structure 222 is less than 5 ⁇ m, such as approximately 2 ⁇ m on laterally opposite sides for a total of 4 ⁇ m.
  • an LED includes a mesa structure 222 that includes a first bottom cladding layer 110A, a spacer layer 232 over the first bottom cladding layer 110A, a second bottom cladding layer 110B over the spacer layer 232, an active layer 108 over the second cladding layer 110B, and a top cladding layer 106 over the active layer 108.
  • a pillar structure 220 is located below the first bottom cladding layer 110A.
  • the pillar structure 220 is in direct contact with the first bottom cladding layer 110A, is centrally located at, and protrudes from the first bottom cladding layer 110A.
  • the first bottom cladding layer 110A is thicker than the second bottom cladding layer 110B, and the second bottom cladding layer 110B comprises a higher Mg dopant concentration than the first bottom cladding layer 110A.
  • FIGS. 24A-24C are cross-sectional side view illustrations of a method of forming an LED with a plasma treated confinement region in accordance with an example not forming part of the invention.
  • FIG. 24A is a cross-sectional side view illustrations of a bulk LED substrate similar to that used for the formation of the LEDs of FIG. 22 or FIG. 23 .
  • a plurality of patterned mask layers 241 are then formed of the current spreading layer 112 to define the current injection regions of the LEDs to be formed, flowed by a plasma treatments such as N 2 plasma.
  • a nitrogen plasma treatment is performed to create current confinement by creating nitrogen vacancies (V N ) in the p-doped layers (e.g. p-GaN current spreading layer 112, and p-AlGaN cladding layer 110.
  • V N nitrogen vacancies
  • FIG. 24C is a cross-sectional side view illustration of an LED structure including confinement regions 242 within the p-doped layers as a result of the plasma treatment, in which the nitrogen vacancies render to confinement regions 242 insulating and provide lateral confinement of the current. Similar to previously described structures, the LED of FIG. 24C may include top conductive contacts 142 formed on the current spreading layers 104, and bottom conductive contacts formed on the current spreading layers 112. Additionally, the LED structure of FIG. 24C may be combined other sidewall treatments described herein for reduced non-radiative sidewall combination.
  • the display substrate 300 may be a thin film transistor (TFT) display substrate (i.e. backplane) similar to those used in active matrix OLED display panels.
  • FIG. 25A is a side-view illustration of a display panel in accordance with an embodiment.
  • the display substrate is a TFT substrate including working circuitry (e.g. transistors, capacitors, etc.) to independently drive each subpixel.
  • Substrate 300 may include a non-pixel area and a pixel area (e.g.
  • the non-pixel area may include a data driver circuit connected to a data line of each subpixel to enable data signals (Vdata) to be transmitted to the subpixels, a scan driver circuit connected to scan lines of the subpixels to enable scan signals (Vscan) to be transmitted to the subpixels, a power supply line to transmit a power signal (Vdd) to the TFTs, and a terminal line or ring to transmit a terminal signal (e.g. ground or some other low voltage (Vss) or reverse bias, power supply or some other high voltage level (Vdd), current source output, or voltage source output) to the array of subpixels.
  • a terminal signal e.g. ground or some other low voltage (Vss) or reverse bias, power supply or some other high voltage level (Vdd), current source output, or voltage source output
  • the data driver circuit, scan driver circuit, power supply line, and terminal line or ring can all be connected to a flexible circuit board (FCB) which includes a power source for supplying power to the power supply line and a power source terminal line electrically connected to the terminal line or ring.
  • FCB flexible circuit board
  • any of the driver circuits can be located off the display substrate 300, or alternatively on a back surface of the display substrate 300.
  • the working circuitry e.g. transistors, capacitors, etc.
  • microdriver chips 350 bonded to the top surface of the substrate 300 as illustrated in FIG. 25B .
  • the TFT substrate includes a switching transistor T1 connected to a data line from the driver circuit and a driving transistor T2 connected to a power line connected to the power supply line.
  • the gate of the switching transistor T1 may also be connected to a scan line from the scan driver circuit.
  • a patterned bank layer 326 including bank openings 327 is formed over the substrate 300.
  • bank openings 327 correspond to subpixels.
  • Bank layer 326 may be formed by a variety of techniques such as ink jet printing, screen printing, lamination, spin coating, CVD, PVD and may be formed of opaque, transparent, or semitransparent materials.
  • bank layer 326 is formed of an insulating material.
  • bank layer is formed of a black matrix material to absorb emitted or ambient light. Thickness of the bank layer 326 and width of the bank openings 327 may depend upon the height of the LEDs 150 transferred to and bonded within the openings, height of the electrostatic transfer heads, and resolution of the display panel. In an embodiment, exemplary thickness of the bank layer 326 is between 1 ⁇ m - 50 ⁇ m.
  • terminal tie lines 344 and terminal ring 316 may optionally be formed over the display substrate 300.
  • an arrangement of terminal tie lines 344 run between bank openings 328 in the pixel area 304 of the display panel.
  • Terminal tie lines 344 may be formed on the bank layer 326 or alternative, openings 332 may be formed in the bank layer 326 to expose terminal tie lines 344 beneath bank layer 326.
  • terminal tie lines 344 are formed between the bank openings 327 in the pixel area and are electrically connected to the terminal ring 316 or a terminal line in the non-display area. In this manner, the terminal signal may be more uniformly applied to the matrix of subpixels resulting in more uniform brightness across the display panel.
  • a passivation layer 348 formed around the LEDs 150 within the bank openings 327 may perform functions such as preventing electrical shorting between the top and bottom electrode layers 318, 342 and providing for adequate step coverage of top electrode layer 318 between the top conductive contacts 142 and terminal tie lines 344.
  • the passivation layer 348 may also cover any portions of the bottom electrode layer 342 to prevent possible shorting with the top electrode layer 318.
  • the passivation layer 348 may be formed of a variety of materials such as, but not limited to epoxy, acrylic (polyacrylate) such as poly(methyl methacrylate) (PMMA), benzocyclobutene (BCB), polymide, and polyester.
  • passivation layer 348 is formed by ink jet printing or screen printing around the LED devices 156 to fill the subpixel areas defined by bank openings 327.
  • Top electrode layer 318 may be opaque, reflective, transparent, or semi-transparent depending upon the particular application. In top emission display panels the top electrode layer 318 may be a transparent conductive material such as amorphous silicon, transparent conductive polymer, or transparent conductive oxide. Following the formation of top electrode layer 318 and encapsulation layer 346 is formed over substrate 300. For example, encapsulation layer 346 may be a flexible encapsulation layer or rigid layer.
  • one or more LEDs 150 are arranged in a subpixel circuit.
  • a first terminal (e.g. bottom conductive contact) of the LED 150 is coupled with a driving transistor.
  • the LED 150 can be bonded to a bonding pad coupled with the driving transistor.
  • a redundant pair of LEDs 150 is bonded to the bottom electrode 342 that is coupled with the driving transistor T2.
  • the one or more LEDs 150 may be any of the LEDs described herein.
  • a terminal line is electrically coupled with a second terminal (e.g. top conductive contact) for the one or more LEDs.
  • a current can be driven through the one or more LEDs, for example, from the driving transistor T2.
  • the one or more LEDs may be on the drain side of a PMOS driver transistor or a source side of an NMOS driver transistor so that the subpixel circuit pushes current through the p-terminal of the LED.
  • the subpixel circuit can be arranged in a low side drive configuration in which case the terminal line becomes the power line and current is pulled through the n-terminal of the LED.
  • FIG. 26 illustrates a display system 2600 in accordance with an embodiment of the present invention.
  • the display system houses a processor 2610, data receiver 2620, a display 2630, and one or more display driver ICs 2640, which may be scan driver ICs and data driver ICs.
  • the data receiver 2620 may be configured to receive data wirelessly or wired. Wireless may be implemented in any of a number of wireless standards or protocols.
  • the one or more display driver ICs 2640 may be physically and electrically coupled to the display 2630.
  • the display 2630 includes one or more LEDs that are formed in accordance with FIG 18 or 19 described above.
  • the display system 2600 may include other components. These other components include, but are not limited to, memory, a touch-screen controller, and a battery.
  • the display system 2600 may be a television, tablet, phone, laptop, computer monitor, kiosk, digital camera, handheld game console, media display, ebook display, or large area signage display.
  • FIG. 27 illustrates a lighting system 2700 in accordance with an embodiment of the present invention.
  • the lighting system houses a power supply 2710, which may include a receiving interface 2720 for receiving power, and a power control unit 2730 for controlling power to be supplied to the light source 2740. Power may be supplied from outside the lighting system 2700 or from a battery optionally included in the lighting system 2700.
  • the light source 2740 includes one or more LEDs that are formed in accordance with FIG 18 or 19 described above.
  • the lighting system 2700 may be interior or exterior lighting applications, such as billboard lighting, building lighting, street lighting, light bulbs, and lamps.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Led Devices (AREA)

Claims (14)

  1. Une LED comprenant :
    une couche de diode p-n (115) comprenant :
    une couche dopée supérieure (104, 106) dopée avec un premier type de dopant ;
    une couche dopée inférieure (110, 112) dopée avec un second type de dopant, opposé du premier type de dopant ;
    une couche active (107, 108, 109) entre la couche dopée supérieure et la couche dopée inférieure,
    dans laquelle la couche active comprend une pluralité de couches de puits quantique (107) et une pluralité de couches de barrière quantique (109) ; et
    un profil de dopant du second type de dopant qui s'étend au travers de régions externes (1801, 1901) de la couche dopée inférieure ainsi que de régions externes (1802, 1902) de la pluralité de couches de puits quantique et de la pluralité de couches de barrière quantique, les profils de dopant ne s'étendant pas au travers de régions internes de la couche dopée inférieure, de la pluralité de couches de puits quantique et de la pluralité de couches de barrière quantique ;
    dans laquelle les compositions des régions externes de la pluralité de couches de puits quantique et de la pluralité de couches de barrière quantique qui se recouvrent avec le profil de dopant sont mélangées entre elles ;
    dans laquelle la pluralité de couches de puits quantique sont contraintes en compression ; et
    des parois latérales de couche de diode p-n (153) couvrant l'étendue de la couche dopée supérieure, de la couche active, de la couche dopée inférieure ; et dans laquelle les bords latéraux (151) de la couche active sont confinés en interne à l'intérieur des parois latérales de couches de diode p-n.
  2. La LED de la revendication 1, dans laquelle chaque couche de la pluralité de couches de puits quantique est plus mince que chaque couche de la pluralité de couches de barrière quantique.
  3. La LED de la revendication 2, dans laquelle chaque couche de la pluralité de couches de puits quantique a une épaisseur de 2 à 5 nm.
  4. La LED de la revendication 2, dans laquelle chaque couche de la pluralité de couches de barrière quantique et chaque couche de la pluralité de couches de puits quantique comprend du (AlxGa(1-x))yIn(1-y)P, et dans laquelle les régions internes de la pluralité de couches de barrière quantique présentent une concentration en aluminium supérieure aux régions internes de la pluralité de couches de puits quantique.
  5. La LED de la revendication 4, dans laquelle les régions externes de la pluralité de couches de puits quantique et de la pluralité de couches de barrière quantique présentent une largeur de bande supérieure à celle des régions internes pour chaque couche de la pluralité de couches de puits quantique, et dans laquelle les régions externes de la pluralité de couches de puits quantique présentent une concentration en Al supérieure à celle des régions intérieures pour chaque couche de la pluralité de couches de puits quantique.
  6. La LED de la revendication 5, dans laquelle les régions externes de la pluralité de couches de puits quantique présentent une concentration en In inférieure à celle des régions intérieures pour chaque couche de la pluralité des couches de puits quantique.
  7. La LED de la revendication 6, dans laquelle le Δx entre les régions internes de la pluralité de couches de barrière quantique et les régions internes des couches actives est supérieur à 0,6.
  8. La LED de la revendication 6, dans laquelle chaque couche de la pluralité de couches de barrière quantique est en tension, et dans laquelle les régions internes de la pluralité de couches de puits quantique présentent une concentration en In supérieure à celle des régions internes de la pluralité de couches de barrière quantique.
  9. La LED de la revendication 6, dans laquelle chacune des régions internes de la pluralité de couches de puits quantique comprend du GaInP.
  10. La LED de la revendication 6, dans laquelle une dimension latérale maximale entre parois latérales de la couche de diode p-n est de 1 à 300 µm, et de préférence de 1 à 20 µm.
  11. La LED de la revendication 10, dans laquelle le profil de dopant est celui d'un dopant de type p.
  12. La LED de la revendication 11, dans laquelle le dopant de type p est Zn.
  13. La LED de la revendication 12, dans laquelle la couche dopée inférieure est de type p.
  14. La LED de la revendication 13, dans laquelle la couche dopée de dessous est formée de AlInP et présente une concentration de dopant Mg in situ allant de 5×1017 cm-3 à 1,5×1018 cm-3.
EP17737419.6A 2016-06-30 2017-06-23 Structures à del servant à réduire la recombinaison non radiative au niveau de parois latérales Active EP3417490B1 (fr)

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US15/199,803 US9601659B2 (en) 2015-01-06 2016-06-30 LED structures for reduced non-radiative sidewall recombination
US15/444,218 US9865772B2 (en) 2015-01-06 2017-02-27 LED structures for reduced non-radiative sidewall recombination
PCT/US2017/039038 WO2018005286A1 (fr) 2016-06-30 2017-06-23 Structures à del servant à réduire la recombinaison non radiative au niveau de parois latérales

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